US3234241A - Process for preparing 2, 2, 4, 4-tetraalkyl-3-hydroxy-3-butenoic acid beta-lactones - Google Patents

Process for preparing 2, 2, 4, 4-tetraalkyl-3-hydroxy-3-butenoic acid beta-lactones Download PDF

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Publication number
US3234241A
US3234241A US321280A US32128063A US3234241A US 3234241 A US3234241 A US 3234241A US 321280 A US321280 A US 321280A US 32128063 A US32128063 A US 32128063A US 3234241 A US3234241 A US 3234241A
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Prior art keywords
lactone
hydroxy
preparing
lactones
tetraalkyl
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US321280A
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English (en)
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Edward U Elam
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE655214D priority Critical patent/BE655214A/xx
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Priority to US321280A priority patent/US3234241A/en
Priority to DEE27922A priority patent/DE1284420B/de
Priority to FR993140A priority patent/FR1412855A/fr
Priority to GB44903/64A priority patent/GB1086006A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/30—Oxygen atoms, e.g. delta-lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00

Definitions

  • R and R each represent lower alkyl groups of from 1 to 4 carbon atoms, such as methyl, ethyl propyl, isopropyl and butyl as present in lower dialltylketenes such as dirnethylketene, or R and R are joined alkylene groups which together with the carbon atom to which they are attached represent a saturated carbocyclic ring of to 6 carbon atoms, e.g. as in tetramethylene ketene and pentamethylene ketene.
  • R P represents an organic tri valent phosphorus derivative catalyst including a phosphine, phosphite, phosphinite or phosphonite catalyst in which R represents either lower alkyl of l to 4 carbon atoms such as present in the trialkylphosphines such as trimethyl, triethyl, tripropyl and tributyl phosphines, e.g. tributylphosphine (C H P; or R represents lower alkoxy of l to 4 carbon atoms such as present in trialkyl phosphites, such as trimethyl, triethyl, tripropyl and tributyl phosphites, e.g.
  • triethylphosphite (C H O) P dialkyl phosphitcs which are pentavalent phosphorus derivatives are not useful
  • R represents a benzene radical including phenyl and substituted phenyl suchas present in the triarylphosphines, e.g. triphenyl phosphine (C H P and tri(chlorophenyl)ph0sphine (Cl-C H P; or R represents a benzoxy radical such as present in triarylphosphites, e.g.
  • trialkylphosphines and triarylphosphines are especially useful as catalysts in the reaction although somewhat more polymerization is obtained using the phosphines with the lower molecular weight dialkylketenes such as dimethylketene.
  • the process is carried out by using catalytic amounts of the phosphine or phosphite compounds (R) P and allowing the reaction mixture to stand at room temperature or at elevated temperature until dimerization is complete after which the dimer can be isolated by distillation especially under reduced pressure as illustrated in the examples below. If desired, the reaction can be run at subor 'superatmospheric pressure but satisfactory results are obtainable by conducting the reaction at atmospheric pressure.
  • the phosphine and phosphite catalysts can be used in catalytic amounts of from about 1% or less of the weight of the charged ketene to an equirnolecular or larger amount.
  • a preferred concentration is about 1 to 5% based on the amount of ketene used.
  • Reaction temperatures of from about 25 C. to the boiling point of the lactone are useful, especially 50 to 175 C.
  • Suitable solvents can be selected from the class of hydrocarbons, ethers, esters, ketones and nitriles, e.g., diethyl ether, tetrahydroiuran, tetrahydropyran, diisopropyl ether, ethylene dichloride, dioxane, benzene, toluene, xylenes, ethylbenzene, chloro-benzene, acetonitrile, ethyl acetate, isopropyl acetate, isobutyl acetate, methyl isobutyrate, di(2-ethylhexyl)phthalate, acetone, methyl isoamyl ketone, and the like.
  • dialkylketenes of formula R R &@O are for example dimethylketene, ethylmethylketene, diethylketene, methylpropylketene, iso'butylethylketene, butylethylketene, tetramethyleneketene and pentamethyleneketene.
  • Example I Five grams of triethyl phosphite were placed in a 1-liter three-necked flask which was fitted with a Dry lce-cooled reflux condenser, thermometer, inlet for dimethylketene, and a magnetic stirrer. Stirring was started and dimethylketene was passed in. A strongly exothermic reaction occurred and the temperature rose spontaneously to to C. and remained there until the d-irnethylketene stream was shut off. A total of approximately 300 grams of product had collected.
  • Example 2 The procedure of Example 1 was repeated except that 5 g. of triphenyl phosphite (C H OMP was used as the catalyst. The generator was shut down after about 250 ml. of dimethylketene had been collected. reaction in this case was only slightly exothermic and some solid tetramethyl-1,3 cyclobutanedione was formed. The liquid present was taken up in ether and separated from the solid by filtration. Gas chromatography of the filtrate indicated that 3-hydroxy-2,2,4-trimethyl-3-pentenoic acid B-lactone was present.
  • C H OMP triphenyl phosphite
  • Example 3 The procedure of Example 1 was repeated with g. of triphenylphosphine (C H P dissolved in 50 ml. of xylene as the catalyst. A quantity of sticky polymer was formed in this reaction, but gas chromatography of the liquid portion of the product indicated that S-hydroxy- 2,2,4-trimethyl-3-pentenoic acid B-lactone was also present.
  • triphenylphosphine C H P dissolved in 50 ml. of xylene
  • Example 4 Ten grams of triethyl phosphite (C H O) P was placed in a 250 ml. three-necked flask equipped with a magnetic stirrer, reflux condenser, thermometer, and a dropping funnel, and 100 g. of butylethylketene was added gradually. An initial highly exothermic reaction carried the temperature to 140 C. The mixture was heated to 165+70 C. overnight. Distillation of the product gave 71 g. boiling from 12'16 C. at 2.5-3 mm., 11;, l.45511.4554.
  • Example 5 The infrared absorption spectrum of this material indicated that it was 2-butyl-2,4adiethyl-3-hydroxy-3-octenoic acid li-lactone, having the formula Example 5
  • the procedure of Example 3 was repeated except using 5 g of tributylphosphine as the catalyst to obtain some 3-hydroxy-2,2,4-trimethyl-3-pentenoic acid fi-lactone and considerable polymer. Monoand dibutylphosphine give similar results.
  • Example 6 The procedure of Example 3 was followed except using 5 ml. of diphenyl decyl phosphite as catalyst. A smaller amount of 3 hydroxy-2,2,4-trimethyl-3-pentenoic acid 18- lactone was formed.
  • Example 8 The procedure of Example 6 wasfollowed except using 5 ml. of dibutyl phenyl phosphonite, (C H O) PC H as the catalyst. The product contained 89% of S-hydroxy 2,2,4-trimethyl-3-pentenoic acid B-lactone and 11% of 2,2,4,4-tetramethyl- 1,3-cyclobutanedione.
  • Example 9 Substitution a butyl diphenylphosphinite as the catalyst in the procedure of Example 8 gives similar results.
  • Example A sample of pentamethyleneketene was dimerized inthe presence of a catalytic amount of triethyl phosphite.
  • the characteristic absorption bands of an unsaturated The A fi-lactone were detected in the infrared spectrum of the reaction product.
  • Example 11 Approximately 5 ml. of freshly distilled butylethylketene was placed in a test tube and a drop of the organic trivalent phosphorus derivative catalyst, hexamethylphosphorous triamide, P[N(CH was added. The mixture became hot and gradually set to a sticky solid. Although this material was mostly polymeric, its infrared spectrum contained a band at 535 which is a highly characteristic feature of the spectra of 2,2,4-,4-tetraalky1- 3-butenoic acid B-lactones. In addition to this band, all of the principal bands of the spectrum of an authentic specimen of the fl-lactone dimer of butylethylketene were present.
  • a process of preparing a 9-lactone which comprises contacting a disubstituted ketene having the general formula wherein R and R are selected from the class consisting of lower alkyl and alkylene groups which together with the carbon atom to which they are attached form a saturated carbocyclic ring of 5 to 6 carbon atoms, with a catalytic amount of a member of the class consisting of phosphine, phosphite, phosphinite and phosphonite compounds having the formula wherein R represents a member of the class consisting of lower alkyl, lower alkoxy, a benzene radical and a benzoxy radical.
  • a process of preparing a S-lactone which comprises contacting a lower dialkylketene with a catalytic amount of a lower trialkylphosphine.
  • a process of preparing a ,B-lactone which comprises contacting dimethylketene with a catalytic amount of tributylphosphine thereby forming 3-hydroxy-2,2,4-trimethyl-3-pentenoic acid ,B-lactone.
  • a process of preparing a fi-lactone which comprises contacting dimethylketene .With a catalytic. amount of triphenylphosphine thereby forming 3-hy-droxy-2,2,4-trimethyl-31pentenoic B-lactone.
  • a process of preparing a B-lactone which comprises.
  • a process of preparing a ,H-lactone which comprises contacting a lower dialkylketene with a catalytic amount of a lower trialkylphosphite.
  • a process of preparing a B-lactone which comprises contacting dimethylketene with a catalytic amount of triethylphosphite thereby forming 3-hydroxy-2,2,4-tri- V methyl-3-pentenoic B-lactone.
  • a process for preparing a ;3-1actone which comprises contacting a lower dialkylketene with a catalytic amount of dibutyl phenyi phosphonite.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US321280A 1963-11-04 1963-11-04 Process for preparing 2, 2, 4, 4-tetraalkyl-3-hydroxy-3-butenoic acid beta-lactones Expired - Lifetime US3234241A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE655214D BE655214A (forum.php) 1963-11-04
US321280A US3234241A (en) 1963-11-04 1963-11-04 Process for preparing 2, 2, 4, 4-tetraalkyl-3-hydroxy-3-butenoic acid beta-lactones
DEE27922A DE1284420B (de) 1963-11-04 1964-10-09 Verfahren zur Herstellung von ungesaettigten ª‰-Lactonen durch Dimerisieren von Ketenen
FR993140A FR1412855A (fr) 1963-11-04 1964-10-29 Nouveau procédé de préparation des bêta-lactones
GB44903/64A GB1086006A (en) 1963-11-04 1964-11-04 Preparing ª‰-lactones

Applications Claiming Priority (1)

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US321280A US3234241A (en) 1963-11-04 1963-11-04 Process for preparing 2, 2, 4, 4-tetraalkyl-3-hydroxy-3-butenoic acid beta-lactones

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114853606A (zh) * 2022-06-18 2022-08-05 衢州伟荣药化有限公司 一种乙酸异丙烯酯的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062836A (en) * 1961-05-09 1962-11-06 Eastman Kodak Co Method of preparing beta-lactones of 2, 2, 4, 4-tetraalkyl-3-hydroxy-3-butenoic acids by catalyzed reaction of dialkylketenes

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062837A (en) * 1962-11-06 Method of preparing
US3089896A (en) * 1963-05-14 Preparation of enolates of
US2450133A (en) * 1947-07-12 1948-09-28 Eastman Kodak Co Process for preparing lactones
US2675372A (en) * 1952-07-09 1954-04-13 Eastman Kodak Co Polymerization of monomeric vinyl compounds
US3074999A (en) * 1958-12-31 1963-01-22 American Cyanamid Co Preparation of dialkyl 2-methyleneglutarates
US3027359A (en) * 1959-06-19 1962-03-27 Jurgeleit Hans Wolfgang Tertiary phosphine polymerization catalysts system
US3161656A (en) * 1961-05-09 1964-12-15 Eastman Kodak Co Unsaturated beta-lactones and method of preparing them
FR1321323A (fr) * 1962-05-07 1963-03-15 Eastman Kodak Co Nouvelles bêta-lactones et procédé pour leur préparation
FR1366081A (fr) * 1963-05-24 1964-07-10 Rhone Poulenc Sa Dicyano-2, 4 butène-1

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062836A (en) * 1961-05-09 1962-11-06 Eastman Kodak Co Method of preparing beta-lactones of 2, 2, 4, 4-tetraalkyl-3-hydroxy-3-butenoic acids by catalyzed reaction of dialkylketenes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114853606A (zh) * 2022-06-18 2022-08-05 衢州伟荣药化有限公司 一种乙酸异丙烯酯的制备方法
CN114853606B (zh) * 2022-06-18 2023-09-29 衢州伟荣药化股份有限公司 一种乙酸异丙烯酯的制备方法

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BE655214A (forum.php)
DE1284420B (de) 1968-12-05

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